Supporting Information

Solid-State Encapsulation and Color Tuning in Films of

Cesium Lead Halide Perovskite Nanocrystals for White

Light Generation

Ilker Torun1, Yemliha Altintas2, Ahmet Faruk Yazici2, Evren Mutlugun3,4,*, M. Serdar Onses1,4,*

1
Department of Materials Science and Engineering, Nanotechnology Research Center
(ERNAM) Erciyes University, Kayseri, 38039, Turkey

2
Department of Materials Science and Nanotechnology Engineering, Abdullah Gul University,
Kayseri, 38080, Turkey

3
Department of Electrical and Electronics Engineering, Abdullah Gul University, Kayseri,
38080, Turkey

4
UNAM – Institute of Materials Science and Nanotechnology, Bilkent University, Ankara,
06800, Turkey

*Address correspondence to: onses@[Link] (M.S.O.), [Link]@[Link] (E.M.)

S1
Synthesis of Red Emitting Quantum Dots

InP-based red emitting quantum dots (QDs) were synthesized according to the previous studies.1-
2
InCl3 (99%, 0.45 mmol), ZnCl2 (98%, 2.2 mmol), and 5 mL of oleylamine (technical grade, 15

mmol) were mixed in a 50 ml flask. The solution was kept under vacuum for an hour at 120 °C.

Then, the temperature of the solution was increased to 180 °C under Ar atmosphere and 250 μL

of tris(dimethylamino)phosphine was quickly injected at 180 °C under vigorous stirring. Core

growth was allowed for 20 min.

Zn- and S-precursors were prepared for ZnS shell coating. 2.2M trioctylphosphine (TOP-S) stock

solution was prepared in glovebox as S-precursor. Zn-precursor was prepared by dissolving 4.5 g

zinc stearate in 20 mL of ODE at 170 °C under argon gas atmosphere to create the Zn-stearate-

ODE stock solution.

In order to start shell growth on core QDs, 1 mL TOP-S was slowly injected at 180 °C just after

the core growth and kept for 40 min at the same temperature. Then the temperature of the

solution was increased to 200 °C. After waiting for 60 min at this temperature, 4 mL Zn-stearate-

ODE stock solution was slowly added into the mixture and the temperature was increased to 220

°C and waited for 30 min. 0.7 mL TOP-S solution was slowly injected and the temperature was

set to 240 °C. Following 30 min waiting time, 2 mL Zn-stearate-ODE solution was slowly

introduced to the reaction and the temperature was raised to 260 °C. At the end of the 30 min, the

reaction was finalized and quickly cooled down to room temperature. Cleaning process was

carried out by using acetone and methanol mixture. After two times cleaning, precipitated

semiconductor nanocrystals were dissolved in hexane or toluene.

S2
Fabrication of WLED

White light emitting diode (WLED) was fabricated by hybridizing the green (PNCs) and red

emissive InP-based quantum dots as color converters on top of a commercial blue LED.

Although InP/ZnS red emitting quantum dots are not affected by the FAS exposure, separate

glass slides were used for each layers. Both green and red quantum dots were drop-casted on a

freshly cleaned glass by spotting a 20 L droplet. Once the glass slides were dried, red and green

color converters were placed, the former below the latter, on a commercial InGaAs blue LED.

The spectrometer probe was placed normal to the hybridized structure to track the progressive

change in the spectrum.

S3
 (a)

(b)

Br : Cl = 12.09

(c)

Br : Cl = 9.76

Figure S1. Energy-dispersive X-ray (EDX) spectroscopy analysis of PNC films. a) Drop-cast

films of PNC films on a freshly cleaned silicon substrate. b) FAS vapor deposition for 10 s on

the drop-cast films of PNC films. c) FAS vapor deposition for 60 s on the drop-cast films of PNC

films.

S4
 (a)

(b)

(c)

Figure S2. FE-SEM images of the films of PNCs a) before and b,c) after deposition of FAS for

b) 10 s, c) 60 s.

S5
Calculation of the quantum efficiency

The quantum efficiency of the films was recorded using the Hamamatsu C9920-12 external

quantum efficiency (EQE) measurement system equipped with an integrating sphere, by

measuring the electroluminescence spectrum of the bare LED before and after nanocrystal film

hybridization, followed by the calculation of the ratio of the emitted light by the nanocrystal film

to the absorbed blue portion of the light. The bare film of CsPbBr3 yields 44.6% quantum yield

while after FAS deposition the quantum yield decreases to 28.5%.

25000 Blue LED

Film of CsPbBr3

20000
After FAS
Intensity (a.u.)

15000

(523)
10000 (509)

5000

0
400 425 450 475 500 525 550 575
Wavelength (nm)

Figure S3. Photoluminescence spectra for the blue LED, film of CsPbBr3, and film of CsPbBr3

after deposition of FAS

S6
 497 505 509 511

Film of CsPbBr3

Normalized PL Intensity (a.u.)

100
FAS Deposition Time = 5s
FAS Deposition Time = 15s
80 FAS Deposition Time = 30s

60

40

20

0
450 475 500 525 550 575 600
Wavelength (nm)

Figure S4. Photoluminescence spectra of the film of CsPbBr3 before and after deposition of FAS

for different durations of exposure to FAS vapor. Films of CsPbBr3 were deposited by spin-

coating at 4000 rpm on a silicon substrate from PNCs dispersed in hexane at a concentration of

30 mg/mL.

S7
 FAS deposition 60 s
0s

Normalized PL Intensity (a.u.)

488 nm 516 nm 15 s
25 s
31 s
38 s
45 s
66 s
85 s
112 s
190 s
286 s
422 s
585 s

460 480 500 520 540 560

Wavelength (nm)

Figure S5. Photoluminescence spectra of the film of CsPbBr3 NCs were shown before and after

deposition of FAS for 60 s. The time indicates the duration after the beginning of the FAS

deposition. The photoluminescence measurements were simultaneously performed with the

deposition of FAS and continued following termination of the FAS deposition. The films of the

nanocrystals were deposited on the hydrophobized substrate by spotting a 10 L drop of PNCs

dispersed in hexane at a concentration of 30 mg/mL.

S8
 1,0

Normalized PL Intensity (a.u.)

0,8

0,6

0,4

0,2 Film of CsPbBr3

FAS Deposition Time = 60s
0,0
0
00:00 15
00:15 30
00:30 45
00:45 60
01:00
t (min)

Figure S6. Air stability of PNCs films with and without FAS deposition. The variation of the PL

intensity as a function of time in air. The deposition of FAS was performed in air for 60 s.

Au
Si
% Transmittance

Si-O-Si

Si-O-Si

500 1000 1500 2000 2500 3000 3500 4000

Wavenumber (cm-1)

Figure S7. FTIR spectrum of the gold-coated silicon substrate following deposition of FAS for

30 s.

S9
Table S1. Thickness and water contact angles on silicon and gold coated silicon substrates. Th.

refers to the thickness. C.A. refers to the water contact angle. The washing was performed in

water under sonication for 2 min.

Before FAS After FAS After washing

Th. C.A Th. C.A Th. C.A (Si / Au)

Si - 2° 7.5 nm 111° 2.30 nm 109°

Au film on Si - 60° 7.4 nm 111° - 60°

Calculation of the chromaticity coordinates

Chromaticity (x,y) coordinates were calculated by using the spectral power distribution (SPD) of

the light and CIE color matching functions. Integrating the product of SPD and color matching

̅ 𝑌̅, 𝑍̅).
functions (𝑥̅ , 𝑦̅, 𝑧̅) over 380 nm to 780 nm separately, gave tristimulus values (𝑋,

780
𝑋=∫ 𝑆𝑃𝐷(𝜆)𝑥̅ (𝜆)𝑑𝜆
380

780
𝑌=∫ 𝑆𝑃𝐷(𝜆)𝑦̅(𝜆)𝑑𝜆
380

780
𝑍=∫ 𝑆𝑃𝐷(𝜆)𝑧̅(𝜆)𝑑𝜆
380

Then, the chromaticity coordinates were calculated as:

𝑋 𝑌
𝑥= 𝑎𝑛𝑑 𝑦 =
𝑋+𝑌+𝑍 𝑋+𝑌+𝑍
Following the mentioned procedure, any visible light could be mapped on 2-dimensional CIE

chromaticity diagram.

S10
Table S2. Color coordinate of the WLED spectrum on CIE diagram given in Figure 6.

Time x y CCT
t1 0.2978 0.3724 4391
t2 0.2863 0.3573 3959
t3 0.2815 0.3491 3760
t4 0.2731 0.2488 2615
t5 0.2757 0.3393 3514
t6 0.269 0.327 3221
t7 0.2656 0.2972 2807
t8 0.2672 0.2748 2606
t9 0.2705 0.2323 3753
t10 0.2685 0.205 -

References

[1] Tessier, M. D.; Dupont, D.; De Nolf, K.; De Roo, J.; Hens, Z., Economic and Size-Tunable
Synthesis of InP/ZnE (E= S, Se) Colloidal Quantum Dots. Chem. Mater. 2015, 27, 4893-4898.

[2] Altıntas, Y.; Talpur, M. Y.; Mutlugün, E., Efficient Förster Resonance Energy Transfer
Donors of In (Zn) P/ZnS Quantum Dots. J. Phys. Chem. C 2017, 121, 3034-3043.

S11